钙改性对生物炭中溶解性有机质与Cd(Ⅱ)结合的影响

doi:10.16258/j.cnki.1674-5906.2025.07.012

生态环境学报 ›› 2025, Vol. 34 ›› Issue (7): 1121-1132.DOI: 10.16258/j.cnki.1674-5906.2025.07.012

• 研究论文【环境科学】 • 上一篇下一篇

钙改性对生物炭中溶解性有机质与Cd(Ⅱ)结合的影响

贺环¹^,²(), 周丹丹¹^,²^,^*(), 马芷萱¹^,², 李芳芳¹^,², 秦珊珊¹^,², 豆思娴¹^,²

1.昆明理工大学环境科学与工程学院，云南昆明 650500
2.云南省土壤固碳与污染控制重点实验室，云南昆明 650500

收稿日期:2025-01-08 出版日期:2025-07-18 发布日期:2025-07-11
通讯作者: *E-mail: 01yongheng@163.com
作者简介:贺环（1994年生），女，硕士研究生，主要研究方向为生物炭环境效应及污染物环境行为研究。E-mail: 1639477032@qq.com
基金资助:
国家自然科学基金青年科学基金项目(41703121);云南省基础研究计划项目(202301AT070472);昆明理工大学人才启动项目(KKSY201722006)

Effect of Calcium Modification on the Binding of Biochar-derived Dissolved Organic Matter with Cd(II)

HE Huan¹^,²(), ZHOU Dandan¹^,²^,^*(), MA Zhixuan¹^,², LI Fangfang¹^,², QIN Shanshan¹^,², DOU Sixian¹^,²

1. Faculty of Environmental Science & Engineering, Kunming University of Science & Technology, Kunming 650500, P. R. China
2. Yunnan Key Laboratory of Soil Carbon Sequestration and Pollution Control, Kunming 650500, P. R. China

Received:2025-01-08 Online:2025-07-18 Published:2025-07-11

摘要/Abstract

摘要：

钙改性生物炭（CaBC）具有比表面积大、官能团种类丰富、矿质元素含量高等特性，对镉污染修复效果好。然而，生物炭施用过程中释放具有显著流动性的溶解性有机质（BDOM）会影响Cd(Ⅱ) 的环境行为。目前，关于钙改性生物炭中BDOM的释放特性及与其Cd(Ⅱ) 的结合特征尚不清晰。采用平行因子和二维相关光谱分析研究钙改性对生物炭BDOM特性的影响，其结果表明：1）钙改性使生物炭BDOM释放量显著增加，尤其是芳香性、疏水性及较大分子量组分；2）钙改性增加了类腐殖酸的相对分布并使其最先释放，但其抑制了类蛋白质的释放速度且类蛋白质含量和相对分布减少。BDOM与Cd(Ⅱ) 的络合实验结果表明：1）钙改性生物炭BDOM中类富里酸与Cd(Ⅱ) 结合速度最快，这与类富里酸相对分布最高有关；2）钙改性提高类蛋白质与Cd(Ⅱ) 的络合能力，但与Cd(Ⅱ) 的结合比例降低，这与改性后类蛋白质含量和相对分布较少有关；3）分子量和芳香性的增加促使BDOM与Cd(Ⅱ) 络合能力及形成的络合物稳定性增加。该研究有助于了解钙改性对BDOM与Cd(Ⅱ) 的结合特征的影响，并为钙改性生物炭在镉污染修复方面的应用提供参考依据。

关键词: 钙改性生物炭, 溶解性有机质, 光谱分析, 镉, 络合

Abstract:

Calcium-modified biochar (CaBC) has a large specific surface area, a rich variety of functional groups, and a high content of mineral elements, which promote the effective remediation of cadmium pollution. However, the release of dissolved organic matter (BDOM) with significant fluidity during biochar application affects the environmental behavior of Cd(II). Currently, the release characteristics of calcium-modified BDOM and its binding to Cd(II) remain largely unknown. In this study, we investigated the effects of calcium modification on the BDOM characteristics using parallel factor analysis and two-dimensional correlation spectroscopy. The results indicated that 1) calcium modification significantly increased BDOM release, especially for aromatic, hydrophobic, and larger molecular weight components; 2) calcium modification enhanced the relative abundance of humic-like substances and promoted their first release, but inhibited the release rate of protein-like components, leading to a reduction in their content and relative abundance. The experimental results on the complexation of BDOM with Cd(II) indicated that: 1) the fulvic-like fraction of calcium-modified BDOM binds to Cd(II) at the fastest rate, which is related to its highest relative distribution; 2) calcium modification enhances the complexation ability of protein-like substances with Cd(II), but the proportion of binding with Cd(II) decreases, which is associated with a lower content and relative distribution of protein-like substances after modification; and 3) the increase in molecular weight and aromaticity enhances the complexation capacity of BDOM with Cd(II) and the stability of the formed complexes. This study is helpful in understanding the effect of calcium modification on the binding characteristics of BDOM and its Cd(II), and provides a reference for the application of calcium-modified biochar in cadmium pollution remediation.

Key words: calcium modified biochar, dissolved organic matter, spectral analysis, cadmium, complexation

中图分类号:

贺环, 周丹丹, 马芷萱, 李芳芳, 秦珊珊, 豆思娴. 钙改性对生物炭中溶解性有机质与Cd(Ⅱ)结合的影响[J]. 生态环境学报, 2025, 34(7): 1121-1132.

HE Huan, ZHOU Dandan, MA Zhixuan, LI Fangfang, QIN Shanshan, DOU Sixian. Effect of Calcium Modification on the Binding of Biochar-derived Dissolved Organic Matter with Cd(II)[J]. Ecology and Environmental Sciences, 2025, 34(7): 1121-1132.

图/表 11

表1 生物炭基本理化性质及元素组成

Table 1 Basic physicochemical properties and elemental composition of biochar

生物炭	基本理化性质				元素组成/%
生物炭	pH	灰分质量分数/%	比表面积/(m²·g⁻¹)	孔体积/(cm³·g⁻¹)	C	H	O	N	H/C	O/C	(O+N)/C
CaBC	6.80	21.07	4.36	0.012	53.08B	4.28A	19.95A	1.37B	0.97A	0.28A	0.30A
BC	7.55	21.02	3.08	0.010	57.84A	4.23A	16.67B	1.71A	0.88B	0.22B	0.24B

图1 生物炭的傅里叶变换红外光谱图（FTIR）

Figure 1 Fourier Transform Infrared (FTIR) spectrum of biochar

表2 BDOM释放动力学模型参数

Table 2 Parameters of BDOM release kinetics model

生物炭	准一级动力学 ln(Q_e−Q_t)=lnQ_e−K₁t			准二级动力学 t/Q_t=1/K₂×Q_e²+t/Q_e			Elovich Q_t=a+blnt
生物炭	Q_e/(mg·g⁻¹)	K₁/(mg·g⁻¹·h⁻¹)	r²	Q_e/(mg·g⁻¹)	K₂/(mg·g⁻¹·h⁻¹)	r²	a/(mg·g⁻¹)	b/(mg·g⁻¹·h⁻¹)	r²
CaBC	10.54	0.88	0.791	11.04	0.13	0.957	6.86	1.13	0.981
BC	3.78	0.61	0.735	4.34	0.15	0.892	1.84	0.69	0.999

图2 BDOM累积释放含量动力学曲线所有数值均为平均值±标准差（n=3）；不同大写字母表示相同时间不同BDOM间差异显著；不同小写字母表示同一BDOM在不同释放时间之间差异显著（p<0.05）；下同

Figure 2 Kinetic curve of cumulative release content of BDOM

图3 BDOM的紫外特征参数变化规律

Figure 3 Variation pattern of UV characteristic parameters of BDOM

表3 BDOM的pH值、离子态钙和络合态钙浓度

Table 3 BDOM pH value, ionic calcium and complex calcium concentration

生物炭	时间	pH值	离子态钙质量浓度/ (mg·L⁻¹)	络合态钙质量浓度/ (mg·L⁻¹)
CaBC	1	6.00	160.90	175.79
CaBC	127	7.59	61.54	15.73
BC	1	6.73	6.27	2.13
BC	127	8.15	3.80	2.67

图4 BDOM在释放过程中同步/异步图

Figure 4 Synchronous/asynchronous diagram of BDOM during release

图5 BDOM中PARAFAC鉴定各组分荧光光谱图

Figure 5 Fluorescence spectrum of each component identified by PARAFAC in BDOM

图6 BDOM中各荧光组分Fmax值和相对分布

Figure 6 Fmax values and relative distribution of fluorescence components in BDOM

图7 BDOM与Cd(Ⅱ) 络合的二维相关光谱

Figure 7 Two-dimensional correlation spectrum of BDOM complexed with Cd(Ⅱ)

表4 BDOM与Cd(Ⅱ)络合修正模型参数

Table 4 BDOM and Cd(Ⅱ) complexation modified model parameters

生物炭	t/h	BDOM荧光组分	lgK	f/%	r²
CaBC	1	C1	4.67	43.07	0.903
		C2	4.43	7.45	0.962
		C3	4.38	13.99	0.900
	127	C1	5.04	30.19	0.831
		C2	4.45	2.93	0.886
		C3	4.63	5.82	0.816
BC	1	C1	4.27	53.21	0.993
		C2	4.42	7.58	0.976
		C3	4.45	35.52	0.970
	127	C1	4.63	23.46	0.968
		C2	No	No	No
		C3	4.62	5.95	0.974

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钙改性对生物炭中溶解性有机质与Cd(Ⅱ)结合的影响

Effect of Calcium Modification on the Binding of Biochar-derived Dissolved Organic Matter with Cd(II)

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